|Publication number||US7263822 B2|
|Application number||US 10/021,346|
|Publication date||Sep 4, 2007|
|Filing date||Dec 19, 2001|
|Priority date||Dec 28, 2000|
|Also published as||CA2366333A1, DE10065473A1, DE50107979D1, EP1219795A2, EP1219795A3, EP1219795B1, US20020083699|
|Publication number||021346, 10021346, US 7263822 B2, US 7263822B2, US-B2-7263822, US7263822 B2, US7263822B2|
|Inventors||Michael Bender, Signe Unverricht|
|Original Assignee||Basf Aktiengesellschaft|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (16), Non-Patent Citations (2), Referenced by (9), Classifications (20), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The present invention relates to a process for the catalytic conversion of fuel, a process for removing oxides of nitrogen from exhaust gases of internal combustion engines and a converter suitable for this purpose.
The technical development of directly injected gasoline and diesel engines operated with a lean mixture has led to a reduction in fuel consumption in recent years. As a result of this trend, the CO2 emission from mobile sources can in future be permanently reduced without losses of power and mineral oil resources can be saved. The disadvantage of the operation of internal combustion engines using a lean mixture is however the formation of oxides of nitrogen (NOx) owing to the large oxygen excess in the combustion chamber. Typically, the NOx concentrations in the engine exhaust gas are a few hundred ppm. The future European exhaust gas standards limit the amount of NOx emitted per kilometer driven to 0.5 g/km from Jan. 1, 2001 and to 0.25 g/km from Jan. 1, 2005. The use of directly injected engines using a lean mixture in car and truck traffic therefore requires efficient removal of oxides of nitrogen from the combustion exhaust gases.
Various possibilities are available for complying with the emission limits:
The technical measures relating to the engine include, for example, exhaust gas recycling to the engine (EGR). The NOx emission can be very efficiently reduced by this measure without losses of motor power since it results in a decrease in the oxygen content in the combustion chamber and hence suppression of the combustion of atmospheric nitrogen. The disadvantage of exhaust gas recycling is the simultaneous increase in the emission of soot particles. This state of affairs referred to as the diesel dilemma means that in practice it is not possible to comply with both limits—NOx as well as soot emission—by means of exhaust gas recycling alone. The effect of EGR apparatuses is partly improved by selective recycling of the oxides of nitrogen. The oxides of nitrogen are temporarily stored and are metered in concentrated form into the intake air of the engine. However, technical measures relating to the engine are not sufficient for achieving the required removal of oxides of nitrogen.
Improved removal of oxides of nitrogen from exhaust gas can be achieved in particular by exhaust gas catalysts in whose active materials the oxides of nitrogen are reacted with a reducing agent. Such catalyst systems rarely act through simple decomposition of the oxides of nitrogen into nitrogen. More frequently, fuel (diesel or gasoline fuel) is used as the reducing agent. The active materials used are as a rule based on noble metals which are applied to an oxidic support material and are arranged as a coating in a molding having a low pressure drop in the exhaust gas line of the vehicle (cf. for example WO 98/40153). In practice, a plurality of catalysts whose temperature ranges for the removal of oxides of nitrogen from the exhaust gas and for the oxidation of uncombusted exhaust gas components are each shifted relative to one another are used in such an exhaust gas system in the case of diesel vehicles. The broadened temperature window results in improved performance of the catalyst arrangement over the entire operating range (urban and nonurban). It is therefore necessary, particularly for diesel vehicles, to mount a catalytic converter close to the engine so that the heat contained in the exhaust gas can heat up the catalyst rapidly and directly and the catalyst rapidly reaches its active temperature.
WO 98/40153, too, describes such a system consisting of two catalysts based on noble metals. At conversions of ≧80% of the hydrocarbon and ≧70% of CO, an NOx degradation of 26% is achieved. However, the reaction in the exhaust gas of an engine operated with a lean mixture has the disadvantage that the reaction of NOx with the fuel used as a reducing agent competes with its combustion in the oxygen excess present. For this reason, only a small part is effectively used for reducing the amount of NOx. The larger part of the fuel is lost without being used. The efficiency can be expressed chemically by the selectivity of the denox reaction. Frequently, the stoichiometric ratios of the denox reaction are neglected so that the selectivity data do not express the efficiency of the hydrocarbon directly. Thus, WO 98/40153 describes, for example, an NOx selectivity of from 0.3 to 1.0, which, when the stoichiometry is taken into account, would correspond to the use of from 1.5 to 5% of the available hydrocarbon propane for the denox reaction. The remaining hydrocarbon is directly combusted.
If these low efficiencies are applied to the NOx reduction with fuel, the theoretical amount of fuel to be used is so high that the fuel dose required for achieving the stipulated EURO IV exhaust gas standard overcompensates the advantageous consumption of the engine operated using a lean mixture. However, the fuel dose can be used neither economically nor technically in an expedient manner since the high heat of combustion of the fuel heats up the exhaust gas catalyst to such an extent that total combustion prevails. In any case, the competing total combustion of the reducing agent limits the NOx degradation so that the EURO IV standard cannot be achieved in this manner.
It is desirable to remove oxides of nitrogen reductively in the lean exhaust gas. Organic substances can be used as selective reducing agents for the catalytic removal of oxides of nitrogen from the exhaust gas of internal combustion engines. For example, in EP-A-0 537 942, the NOx reduction over highly acidic γ-Al2O3 with the aid of organic substances is described. The publication states that alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, ethers and esters can be used as such reducing agents. The publication furthermore describes the metering of these substances into the exhaust gas stream upstream of the NOx reduction catalyst via a nozzle. The nozzle physically atomizes, i.e. disperses, liquid or gaseous reactants. The NOx reduction with propylene as reducing agent is described in detail. The NOx degradation values of up to 80% are achieved only at temperatures above 500° C. This fact is disadvantageous since the temperature of the exhaust gas, in particular of diesel engines, is 100-400° C. and hence substantially below the NOx degradation temperature described in EP-A-0 537 942.
The reducing agents can be provided either by carrying in a separate tank or by on-board production from a precursor. The latter variant has advantages since the vehicle fuel can be used as the precursor so that there is also no need for an expensive on-board infrastructure for carrying the precursor. Thus, JP-A-112 44663 describes a process in which the hydrocarbon-containing exhaust gas is passed first over a partial oxidation catalyst and then over the actual NOx reduction catalyst. The partial oxidation catalysts described are titanium oxides which have been doped with various transition metals. Noble metal-containing active materials are used for the actual NOx reduction. The disadvantage of this process is the fact that the temperature of the partial oxidation catalyst is not constant since said catalyst is alternatively heated and cooled by the temperature of the exhaust gas stream. The temperature of the catalyst system and hence the denox performance thus depends on the operating point of the engine.
JP-A-100 005 46 describes a similar process. Here too, the hydrocarbon used for the NOx reduction is partially oxidized beforehand. For this purpose, at least a part of the exhaust gas or a separate air stream is mixed with hydrocarbon and an oxygen-containing, organic substance and this mixture is oxidized to aldehydes in an oxidation unit. The residence time of the gas stream in the oxidation reactor is set at 0.05-1 second. The aldehydes are passed into the main exhaust gas stream and reacted with the oxides of nitrogen contained therein over an NOx reduction catalyst. The active materials consist of various transition metals (Ag, Co, Ni) supported on γ-Al2O3. The disadvantage of these systems is that they exhibit NOx degradation only at temperatures above 350° C. It is true that the NOxdegradation temperature can be reduced considerably by using Pt/Ce as dopant. However, the optimum temperature for operating the oxidation unit is still very high at 500° C. Engine components suffer as a result of the considerable heat radiation of the oxidation unit, and the autothermal operation of this oxidation unit is not possible. Such a converter must be externally heated.
It is an object of the present invention to provide a process for the catalytic conversion of fuel and for removing oxides of nitrogen from exhaust gases of internal combustion engines, which process avoids the disadvantages of the existing processes.
We have found that this object is achieved, according to the invention, by a process for the catalytic conversion of fuel for removing oxides of nitrogen from exhaust gases of internal combustion engines, in which fuel and a part-stream of the exhaust gas or of the intake air are converted in a converter, wherein the fuel and the part-stream of the exhaust gas or of the intake air are fed separately from one another into the converter and the fuel is vaporized in the converter.
The term fuel describes all conventional fuels, such as gasoline and diesel fuels, and other corresponding mineral oil distillates. In particular, diesel fuel is understood by this term.
The term internal combustion engine relates in general to engines which are driven by combustion of fuel. In particular it relates to gasoline or diesel engines, particularly diesel engines, especially engines operated using a lean mixture.
In the converter, the fuel is converted. The conversion may comprise cracking, dehydrogenation or partial oxidation. Preferably, the fuel is dehydrogenated or partially oxidized, especially partially oxidized. The fuel is preferably at least partially oxidized to carboxylic acids and/or carboxylic anhydrides. In particular, the fuel is at least partially oxidized to maleic acid and/or maleic anhydride. The reaction preferably leads very substantially to maleic acid or maleic anhydride.
However, the converter product stream may also contain carbon monoxide or hydrogen or a mixture of the two gases.
We have found that this object is also achieved, according to the invention, by a process for removing oxides of nitrogen from exhaust gases of internal combustion engines, wherein first a process as described above for the catalytic conversion of fuel is carried out, and the product stream from the converter is combined with the exhaust gas of the internal combustion engine and is reacted over a catalyst for the degradation of the oxides of nitrogen.
In particular, maleic acid or maleic anhydride is reacted with the oxides of nitrogen (NOx), the oxides of nitrogen being reduced and the maleic anhydride or the maleic acid being oxidized.
The reaction for the degradation of the oxides of nitrogen is preferably carried out over a catalyst whose active material does not promote the total oxidation of maleic anhydride. The active material of the catalyst therefore contains no Cr, Mn, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt or Cu. The catalyst for the degradation of the oxides of nitrogen thus has no combustion activity, in contrast to the noble metal-containing catalysts usually used.
The catalyst for the degradation of the oxides of nitrogen preferably contains at least one oxide of a metal of the first to fourth main group of the Periodic Table of the Elements, in particular of aluminum. Especially, the catalyst contains γ-Al2O3. It may also consist of γ-Al2O3.
The catalyst does not promote total combustion of organic substances in the temperature window of from 100 to 600° C., preferably from 150 to 500° C., in particular from 200 to 400° C.
The catalyst may contain tin oxide in an amount of from 0 to 70, preferably from 0 to 50, in particular from 0 to 30, % by weight (based on the total weight of the catalyst).
The catalyst may have a monolithic honeycomb shape, preferably in the form of an extruded and subsequently calcined active material.
The product stream obtained after the reaction over the catalyst for the degradation of the oxides of nitrogen may additionally be further reacted over a noble metal-containing catalyst for the oxidation of remaining organic compounds.
In comparison with known processes, according to the invention the reaction of oxides of nitrogen with hydrocarbons is separated into two steps. First, the fuel (hydrocarbons) is oxidized to maleic acid (anhydride) and, in a subsequent step, the oxides of nitrogen and maleic acid (anhydride) are reacted over γ-Al2O3 to give nitrogen and preferably carbon dioxide. The formation of maleic acid (anhydride) can be carried out under steady-state conditions which are optimally chosen (temperature, space velocity, etc.) so that a maximum maleic acid (anhydride) yield is possible. Only then is the product mixed with the exhaust gas, whose composition differs depending on the operation of the engine, and further reacted. This makes it possible to carry out the removal of oxides of nitrogen, in particular in engines operated using a lean mixture, cheaply and with high yields.
The present invention also relates to a converter for the catalytic conversion of fuel, comprising a vaporization space and a conversion space connected thereto, the vaporization space having separate feeds for exhaust gas or intake air and fuel, the conversion space having a catalyst for the catalytic conversion of fuel and the vaporization space and the conversion space being connected to one another so that heat transport from the conversion space into the vaporization space is possible.
The converter can be used in the process described above.
The preferred embodiments which follow illustrate the invention:
The reference numerals have the following meanings:
The catalysts for partial reaction and denox reaction were tested in a laboratory apparatus. For this purpose, the active materials in chip form (0.7-1.0 mm) were initially taken in a reactor and externally heated in an oven. To do this, the oven was controlled linearly from 200° C. to 400° C. The gas loading was 20 000 h−1. The synthetic exhaust gas was premixed with a residual O2 content of 10% and a water content of 5%.
The partial oxidation was effected with vaporization of the fuel over an externally heated bed of steatite beads. The yield of maleic anhydride was determined in the gas phase with the aid of an IR spectrometer.
In the experiments for removing oxides of nitrogen from exhaust gas, the catalytic NOx degradation in the cooling phase of the tests was determined with the aid of a chemiluminescence NOx detector. The partial oxidation of diesel to maleic anhydride showed a maximum at 400° C. with a yield of about 30%.
The present invention relates in particular to the improvement of the removal of oxides of nitrogen from the exhaust gas of a directly injected (DI) diesel engine (
According to the invention, the vehicle is preferably operated using three catalysts. First, the diesel fuel provided for the NOx reduction is partially oxidized to maleic anhydride (MAA) in a converter. The MAA-containing product stream is combined with the main exhaust gas stream, and the oxides of nitrogen are reacted with MAA over a denox catalyst to give nitrogen, carbon dioxide and water. MAA residues are oxidized with excess oxygen in a third noble metal-containing catalyst to give CO2 and H2O.
The technical implementation is preferably effected by controlled throttling of the exhaust gas stream (
The control of the gas stream by the throttle valves (16, 20) is effected by means of the engine electronics (18) with the aid of the relevant gas pressure (17, 21) as a measured variable. The amount of the partial gas stream fed in is such that the concentration of diesel fuel in the gas phase in the interior of the converter is constant. An indirect criterion for this is the converter temperature (15) which, in the case of complete conversion of the diesel to MAA, is obtained from the heat of reaction and the heat capacity of the partial gas stream. The converter temperature is kept constant at 400° C. At this temperature, the yield of MAA is maximum. Furthermore, the thermal load of the environment in the engine space is substantially reduced with respect to comparable converters.
The structure of the converter is shown in
The MAA-containing product stream of the converter is combined, upstream of the catalytic converter close to the engine, with the main exhaust gas stream and passes together with this via the catalytic converter close to the engine. In conventional systems, this catalyst contains noble metal-based or transition metal-based active materials. The relevant catalysts are produced by applying an oxidic wash coat to ceramic or metallic honeycomb elements by slip coating, followed by drying and calcination and subsequent impregnation with noble metal or transition metal salt, followed in turn by drying and calcination.
Such expensive catalyst systems can be dispensed with in the case of the catalytic converter close to the engine and intended for the novel denox process described here. Instead, a honeycomb element on which a wash coat of γ-Al2O3 is applied by slip coating and subsequent drying and calcination is preferably used. It is even advantageous to use a solid honeycomb extruded from γ-Al2O3, so that the number of production steps is further reduced. γ-Al2O3 is adequate as active material for the efficient reduction of NOx with MAA. Downstream of the catalytic converter close to the engine is a noble metal-containing underfloor catalyst as already used in conventional systems. This catalyst oxidizes CO and volatile organic components, which would otherwise enter the environment, to CO2 and H2O.
Substantially higher NOx degradation values are achieved by using γ-Al2O3 (C) inactive with respect to combustion. With diesel fuel, degradation values of up to 40% can be achieved here. However, high reaction temperatures of up to 500° C. are required for this purpose, in order to be able to catalytically activate the diesel fuel. For this reason, the NOx degradation in the relevant temperature window is only below 25%. As a result of the partial oxidation of the diesel fuel to MAA, upstream of the NOx reduction over γ-Al2O3, this degradation value improves to 47% at as low as 400° C. (D). It is thus substantially above the values found over platinum- or copper-doped catalysts at 200-400° C.
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|U.S. Classification||60/274, 123/1.00A, 60/301, 60/286, 422/169, 60/303, 123/538, 422/172|
|International Classification||F01N13/02, F01N3/00, F01N3/20, F02M63/02|
|Cooperative Classification||Y02T10/24, F01N2610/04, F01N3/2066, F01N2610/03, F02M63/0225, F01N13/009, F01N13/0093|
|Dec 19, 2001||AS||Assignment|
Owner name: BASF AKTIENGESELLSCHAFT, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BENDER, MICHAEL;UNVERRIGHT, SIGNE;REEL/FRAME:012390/0098
Effective date: 20011025
|Mar 18, 2008||CC||Certificate of correction|
|Apr 11, 2011||REMI||Maintenance fee reminder mailed|
|Sep 4, 2011||LAPS||Lapse for failure to pay maintenance fees|
|Oct 25, 2011||FP||Expired due to failure to pay maintenance fee|
Effective date: 20110904